Crystalline transition metal tungstate

ABSTRACT

A hydroprocessing catalyst or catalyst precursor has been developed. The catalyst is a crystalline transition metal tungstate material or metal sulfides derived therefrom. The hydroprocessing using the crystalline ammonia transition metal tungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/690,184 filed Jun. 26, 2018, the contents of which cited applicationare hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a new catalyst such as hydroprocessingcatalyst. More particularly this invention relates to a crystallinetransition metal tungstate and its use as a hydroprocessing catalyst.Hydroprocessing may include hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

BACKGROUND

In order to meet the growing demand for petroleum products there isgreater utilization of sour crudes, which when combined with tighterenvironmental legislation regarding the concentration of nitrogen andsulfur within fuel, leads to accentuated refining problems. The removalof sulfur (hydrodesulfurization—HDS) and nitrogen(hydrodenitrification—HDN) containing compounds from fuel feed stocks istargeted during the hydrotreating steps of refining and is achieved bythe conversion of organic nitrogen and sulfur to ammonia and hydrogensulfide respectively.

Since the late 1940s the use of catalysts containing nickel (Ni) andmolybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfurremoval. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad,Division of Petroleum Chemistry, 115^(th) Meeting ACS, San Francisco,1949. For several decades now there has been an intense interestdirected towards the development of materials to catalyze the deepdesulfurization, in order to reduce the sulfur concentration to the ppmlevel. Some recent breakthroughs have focused on the development andapplication of more active and stable catalysts targeting the productionof feeds for ultra low sulfur fuels. Several studies have demonstratedimproved HDS and HDN activities through elimination of the support suchas, for example, Al₂O₃. Using bulk unsupported materials provides aroute to increase the active phase loading in the reactor as well asproviding alternative chemistry to target these catalysts.

More recent research in this area has focused on the ultra deepdesulfurization properties achieved by a Ni—Mo/W unsupported‘trimetallic’ material reported in, for example, U.S. Pat. No.6,156,695. The controlled synthesis of a broadly amorphous mixed metaloxide consisting of molybdenum, tungsten and nickel, significantlyoutperformed conventional hydrotreating catalysts. The structuralchemistry of the tri-metallic mixed metal oxide material was likened tothe hydrotalcite family of materials, referring to literature articlesdetailing the synthesis and characterization of a layered nickelmolybdate material, stating that the partial substitution of molybdenumwith tungsten leads to the production of a broadly amorphous phasewhich, upon decomposition by sulfidation, gives rise to superiorhydrotreating activities.

The chemistry of these layered hydrotalcite-like materials was firstreported by H. Pezerat, contribution à l'étude des molybdates hydratesde zinc, cobalt et nickel, C. R. Acad. Sci., 261, 5490, who identified aseries of phases having ideal formulas MMoO₄.H₂O, EHM₂O⁻(MoO₄)₂.H₂O, andE_(2-x)(H₃O)_(x)M₂O(MoO₄)₂ where E can be NH₄ ⁺, Na⁺ or K⁺ and M can beZn²⁺, Co²⁺ or Ni²⁺.

Pezerat assigned the different phases he observed as being Φc, Φx or Φyand determined the crystal structures for Φx and Φy, however owing to acombination of the small crystallite size, limited crystallographiccapabilities and complex nature of the material, there were doubtsraised as to the quality of the structural assessment of the materials.During the mid 1970s, Clearfield et al attempted a more detailedanalysis of the Φx and Φy phases, see examples A. Clearfield, M. J.Sims, R. Gopal, Inorg. Chem., 15, 335; A. Clearfield, R. Gopal, C. H.Saldarriaga-Molina, Inorg. Chem., 16, 628. Single crystal studies on theproduct from a hydrothermal approach allowed confirmation of the Φxstructure, however they failed in their attempts to synthesize Φy andinstead synthesized an alternative phase, Na—Cu(OH)(MoO₄), see A.Clearfield, A. Moini, P. R. Rudolf, Inorg. Chem., 24, 4606.

The structure of Φy was not confirmed until 1996 by Ying et al. Theirinvestigation into a room temperature chimie douce synthesis techniquein the pursuit of a layered ammonium zinc molybdate led to a metastablealuminum-substituted zincite phase, prepared by the calcination of Zn/Allayered double hydroxide (Zn₄Al₂(OH)₁₂CO₃.zH₂O). See example D. Levin,S. L. Soled, J. Y. Ying, Inorg. Chem., 1996, 35, 4191-4197. Thismaterial was reacted with a solution of ammonium heptamolybdate at roomtemperature to produce a highly crystalline compound, the structure ofwhich could not be determined through conventional ab-initio methods.The material was indexed, yielding crystallographic parameters whichwere the same as that of an ammonium nickel molybdate, reported byAstier, see example M. P. Astier, G. Dji, S. Teichner, J. Ann. Chim.(Paris), 1987, 12, 337, a material belonging to a family ofammonium-amine-nickel-molybdenum oxides closely related to Pezerat'smaterials. Astier did not publish any detailed structural data on thisfamily of materials, leading to Ying et al reproducing the material tobe analyzed by high resolution powder diffraction in order to elucidatethe structure. Ying et al named this class of materials ‘layeredtransition-metal molybdates’ or LTMs.

Since the initial reports of unsupported Ni—Mo/W oxidic precursors, U.S.Pat. No. 6,156,695, there have been several reports describing materialswhich, when sulfided, claim to have enhanced hydrotreating activities.U.S. Pat. No. 6,534,437 discloses a process for preparing a mixed metalcatalyst having a powder x-ray diffraction pattern showing reflectionsat approximately 2.53 Angstroms and 1.70 angstroms. U.S. Pat. No.6,534,437 differentiates itself from U.S. Pat. No. 3,678,124 and WO9903578 based on characteristic full width half maximum line widths ofmore resolved reflections, present in WO 9903578, claiming that theinvention of U.S. Pat. No. 6,534,437 possesses a ‘differentmicrostructure’ from prior work, WO 9903578.

U.S. Pat. No. 8,722,563 describes preparing a series of catalystprecursors with compositions comprising at least one Group VI metal andone metal from Group VIII through Group X. One of the comparativeexamples described in the patent yields a comparable powder x-raydiffraction pattern to that obtained in U.S. Pat. No. 6,534,437 and isdescribed as the as-synthesized and dried hexagonal NiWO₄ catalystprecursor.

U.S. Pat. No. 7,648,941 discloses synthetic examples of a series ofdifferent bimetallic materials and states that the bulk bimetalliccatalyst of the invention has a metastable structure and further assertthat the crystalline 2θ structure of the metastable hexagonal NiWO₄phase in the preferred catalysts of the invention have latticeparameters a=2.92 Å, b=2.93 Å, and c=4.64 Å and that bulk catalyst has ametastable hexagonal structure having an X-ray diffraction pattern witha single reflection between 58 and 65°. As a point of reference, thelargest two d-spacings which can be generated in an x-ray diffractionpattern by a hexagonal cell with lattice parameters a=2.92 Å, b=2.93 Å,and c=4.64 Å are 4.64 Å and 2.53 Å.

A. Dias and V. S. T. Ciminelli, J. Eur. Ceramic. Soc, 2001, 21,2061-2065 reported on the thermodynamic calculations and modeling ofhydrothermally synthesized nickel tungstates. They present a series ofcalculated yield diagrams at various synthesis temperatures highlightingthe pH and reagent concentrations which yield NiWO₄. All of theircalculations predict the formation of a nickel tungstate between pH 2and 7.5, with nickel hydroxide being the main product at higher pH's.The authors show the x-ray diffraction patterns for the samples producedat 200, 230 and 260° C. within and without their predicted yield zones.The x-ray diffraction pattern for the NiWO₄ material synthesized at 200°C. can be described as poorly crystalline and the reference asserts thatit is important to note that a crystallized material was obtained at200° C., but with extremely fine particle size indicated by broad X-raydiffraction peaks. The reference asserts this can be explained by theenergy barrier for the precipitation, which is closely related to thenature of the rate-controlling step in the dominant formation process.The reference puts forth that higher reaction temperatures acceleratethe crystallization process because of greater thermal energy toovercome the energy barrier for transformation, and a consequence,materials with higher crystallinity and/or particle size can beobtained. The reference suggests that the phase obtained at 200° C. isessentially a poorly crystalline, nano-wolframite (NiWO₄), and thisconclusion is consistent with calculated yield diagrams of thereference.

Y. Bi, H. Nie, D. Li, S. Zeng, Q. Yang and M. Li, ChemicalCommunications, 2010, 46, 7430-7432 discuss the preparation of NiWO₄nanoparticles as a promising hydrodesulfurization catalyst, stating thatall the reflections in a typical powder x-ray diffraction pattern can beindexed undisputedly to the monoclinic NiWO₄, Wolframite, phase. Thereference asserts that FIG. 1 shows the typical X-ray diffraction (XRD)pattern of the as-made sample and all reflections can be indexedundisputedly to the monoclinic NiWO₄ phase (JCPDS card 72-1189). Thereference concludes that a close examination reveals that thereflections in the XRD pattern are a little broad, indicating thecharacteristic feature of nanosized materials.

SUMMARY OF THE INVENTION

A crystalline transition metal tungstate material has been produced andoptionally sulfided, to yield an active catalyst or catalyst precursorsuch as a hydroprocessing catalyst. The crystalline transition metaltungstate material has a x-ray powder diffraction pattern showing peaksat 11.8, 10.5, 7.8, 7.6, 6.8, 6.4 and 5.7 Å. The crystalline transitionmetal tungstate material has the formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂Owhere ‘A’ is selected from NH₄, H₃O⁺ or combinations thereof; ‘m’ variesfrom 1 to 12, or from 2 to 8, or from 3 to 5; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.5 to 6, or from 0.7 to 4, orfrom 0.8 to 2; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; the material is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A:

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w

Another embodiment involves a method of making a crystalline transitionmetal tungstate material having the formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂Owhere ‘A’ is selected from NH₄, H₃O⁺ or combinations thereof; ‘m’ variesfrom 1 to 12, or from 2 to 8, or from 3 to 5; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.5 to 6, or from 0.7 to 4, orfrom 0.8 to 2; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; the material is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A:

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 wthe method comprising forming an reaction mixture containing sources ofA, M and W; and reacting the mixture at elevated temperatures in an openor sealed vessel and then recovering the crystalline mixed transitionmetal tungstate material. Another embodiment further comprises dryingthe recovered crystalline transition metal tungstate material at atemperature from about 100° C. to about 350° C. for about 30 minutes toabout 48 hours.

Yet another embodiment involves a conversion process comprisingcontacting a sulfiding agent with a material to generate metal sulfideswhich are contacted with a feed at conversion conditions to generate atleast one product, the material comprising: a crystalline transitionmetal tungstate material having the formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂Owhere ‘A’ is selected from NH₄, H₃O⁺ or combinations thereof; ‘m’ variesfrom 1 to 12, or from 2 to 8, or from 3 to 5; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.5 to 6, or from 0.7 to 4, orfrom 0.8 to 2; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material; the material is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A:

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w

In another embodiment, the process further comprising at least one of:sensing at least one parameter of the process and generating a signal ordata from the sensing; or generating and transmitting a signal; orgenerating and transmitting data.

Additional features and advantages of the invention will be apparentfrom the description of the invention, FIGURES and claims providedherein.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is the x-ray powder diffraction pattern of a crystallinetransition metal tungstate material prepared by the method as describedin the Examples.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a crystalline transition metaltungstate composition and a process for preparing the composition. Thematerial has the designation UPM-26, and has an empirical formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂Owhere ‘A’ is selected from NH₄, H₃O⁺ or combinations thereof; ‘m’ variesfrom 1 to 12, or from 2 to 8, or from 3 to 5; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.5 to 6, or from 0.7 to 4, orfrom 0.8 to 2; ‘z’ is a number which satisfies the sum of the valency ofthe cationic species present in the material.

The crystalline transition metal tungstate material composition of theinvention is characterized by having an extended network of M-O-M, whereM represents a metal, or combination of metals listed above. Thestructural units repeat itself into at least two adjacent unit cellswithout termination of the bonding. The composition can have aone-dimensional network, such as, for example, linear chains.

The crystalline transition metal tungstate composition is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A.

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w

The crystalline transition metal tungstate composition of the inventionis further characterized by the x-ray powder diffraction pattern shownin the FIGURE.

The crystalline transition metal tungstate composition can be preparedby solvothermal crystallization of a reaction mixture, typically bymixing reactive sources of tungsten with the appropriate metal ‘M’.

Sources of M, and W include, but are not limited to, the respectivehalide, sulfide, acetate, nitrate, carbonate, sulfate, oxalate, thiols,hydroxide salts, and oxides of M, or W. Specific examples of sources ofM include, but are not limited to, manganese nitrate, manganesechloride, manganese bromide, manganese sulfate, manganese carbonate,manganese sulfide, manganese hydroxide, manganese oxide, copper nitrate,copper chloride, copper bromide, copper sulfate, copper carbonate,copper acetate, copper oxalate, copper sulfide, copper hydroxide, copperoxide, zinc nitrate, zinc chloride, iron bromide, zinc sulfate, zinccarbonate, zinc acetate, zinc oxalate, zinc sulfide, zinc hydroxide,zinc oxide, and any mixture thereof. Additional specific sources includenickel chloride, nickel bromide, nickel nitrate, nickel acetate, nickelcarbonate, nickel hydroxide, cobalt chloride, cobalt bromide, cobaltnitrate, cobalt acetate, cobalt carbonate, cobalt hydroxide, cobaltsulfide, nickel chloride, cobalt oxide, nickel bromide, nickel sulfide,nickel oxide, iron acetate, iron oxalate, iron nitrate, iron chloride,iron bromide, iron sulfate, iron carbonate, iron oxalate, iron sulfide,iron oxide, magnesium chloride, vanadium chloride and any mixturethereof. Yet additional sources include, but are not limited to,tungstates and thioltungstates, such as tungsten trioxide, tungsticacid, tungsten oxytetrachloride, tungsten hexachloride, hydrogentungstate, ammonium ditungstate, sodium ditungstate, ammoniummetatungstate, ammonium paratungstate, sodium ditungstate, sodiumditungstate, sodium metatungstate, sodium paratungstate, and any mixturethereof.

Generally, the process used to prepare the composition of this inventioninvolves forming a reaction mixture wherein the components, such as forexample, Ni, W, NH₄OH and H₂O are mixed together. By way of specificexamples, a reaction mixture may be formed which in terms of molarratios of the oxides is expressed by the formula:MO_(x):AWO_(z):B(NH₃):H₂Owhere ‘M’ is selected from iron, cobalt, nickel, manganese, vanadium,copper, zinc, and combinations thereof; ‘x’ is a number which satisfiesthe valency of ‘M’; ‘A’ represents the ratio of ‘W’ relative to ‘M’ andvaries from 0.5 to 6, or from 0.7 to 4, or from 0.8 to 2; ‘z’ is anumber satisfies the valency of ‘W’; ‘B’ represents the molar ratio of‘NH₃’ and may vary from 0.1 to 100, or from 1 to 50, or from 2.5 to 25;the molar ratio of H₂O varies from 1 to 5000, or from 10 to 300, or from20 to 100.

Once the reaction mixture is formed, the reaction mixture is reacted attemperatures ranging from about 60° C. to about 110° C. for a period oftime ranging from 30 minutes to around 14 days. In one embodiment, thetemperate range for the reaction is from about 60° C. to about 90° C.and in another embodiment the temperature is in the range of from about100° C. to about 110° C. In one embodiment, the reaction time is fromabout 2 to about 4 hours, and in another embodiment the reaction time isfrom about 4 to 7 days. The reaction is carried out under atmosphericpressure or in a sealed vessel under autogenous pressure. In oneembodiment, the synthesis may be conducted in an open vessel. Thecrystalline transition metal tungstate compositions are recovered as thereaction product. Optionally, the recovered crystalline transition metaltungstate material may be dried at a temperature from about 100° C. toabout 350° C. for about 30 minutes to about 48 hours. The recovery maybe by evaporation of solvent, decantation, filtration, orcentrifugation. The crystalline transition metal tungstate compositionsare characterized by the x-ray powder diffraction pattern as shown inTable A above and the FIGURE.

In the art of hydrothermal synthesis of metal oxides, it is well knownthat hydroxide defects occur in metal oxides made by this route, and arelocated either internally as defects or externally as a result of oftenlarge external surface areas that are at least partially hydroxylated.These nonstoichiometric amounts of hydroxide moieties additively,together with the oxide ions, account for the collective valences of themetal ions in the compositions.

In one embodiment, an intermediate may be formed before reacting thereaction mixture. The intermediate is formed by removing at least someof the sources of A, H₂O or NH₃ or both, to generate the intermediatewhich may be a precipitate, or at least a portion of the reactionmixture, or both a precipitate and a portion of the reaction mixture.The intermediate is then reacted as the reaction mixture at atemperature from about 60° C. to about 110° C. for a period of fromabout 30 minutes to 14 days to generate the transition metal tungstatematerial.

Once formed, the crystalline transition metal tungstate may have abinder incorporated, where the selection of binder includes but is notlimited to, anionic and cationic clays such as hydrotalcites,pyroaurite-sjogrenite-hydrotalcites, montmorillonite and related clays,kaolin, sepiolites, silicas, alumina such as (pseudo) boehomite,gibbsite, flash calcined gibbsite, eta-alumina, zirconia, titania,alumina coated titania, silica-alumina, silica coated alumina, aluminacoated silicas and mixtures thereof, or other materials generally knownas particle binders in order to maintain particle integrity. Thesebinders may be applied with or without peptization. The binder may beadded to the bulk crystalline transition metal tungstate composition,and the amount of binder may range from about 1 to about 30 wt % of thefinished catalysts or from about 5 to about 26 wt % of the finishedcatalyst. The binder may be chemically bound to the crystallinetransition metal tungstate composition, or may be present in a physicalmixture with the crystalline transition metal tungstate composition.

At least a portion of the crystalline transition metal tungstate, withor without a binder, or before or after inclusion of a binder, can besulfided in situ in an application or pre-sulfided to form metalsulfides which in turn are used in an application. The sulfidation maybe conducted under a variety of sulfidation conditions such as throughcontact of the crystalline transition metal tungstate with a sulfidingagent such as a sulfur containing stream or feedstream or throughcontact with a gaseous mixture of H₂S/H₂. The sulfidation of thecrystalline transition metal tungstate may be performed at elevatedtemperatures, typically ranging from 50 to 600° C., or from 150 to 500°C., or from 250 to 450° C. The materials resulting from the sulfidingstep, the decomposition products, are referred to as metal sulfideswhich can be used as catalysts in conversion processes. As noted above,at least a portion of the metal sulfides may be present in a mixturewith at least one binder. The sulfiding step can take place at alocation remote from other synthesis steps, remote from the location ofthe conversion process, or remote from both the location of synthesisand remote from location of the conversion process.

As discussed, at least a portion of the crystalline transition metaltungstate material of this invention can be sulfided and the resultingmetal sulfides used as catalysts in conversion processes such ashydrocarbon conversion processes. Hydroprocessing is one class ofhydrocarbon conversion processes in which the crystalline mixedtransition metal tungstate, or metal sulfides derived therefrom, isuseful as a catalyst. Examples of specific hydroprocessing processes arewell known in the art and include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. In one embodiment, a conversion process comprisescontacting the crystalline mixed transition metal tungstate with asulfiding agent to generate metal sulfides which are contacted with afeed stream at conversion conditions to generate at least one product.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range from about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Time with which the feed is incontact with the active catalyst, referred to as liquid hour spacevelocities (LHSV), should be in the range of about 0.1 h⁻¹ to about 10h⁻¹, or about 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets of these rangesmay be employed depending upon the feedstock being used. For example,when hydrotreating a typical diesel feedstock, operating conditions mayinclude from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about410° C., from about 0.25/h to about 5/h, and from about 84 Nm³ H₂/m³ toabout 850 Nm³ H₂/m³ feed. Other feedstocks may include gasoline,naphtha, kerosene, gas oils, distillates, and reformate.

Any of the lines, conduits, units, devices, vessels, surroundingenvironments, zones or similar used in the process may be equipped withone or more monitoring components including sensors, measurementdevices, data capture devices or data transmission devices. Signals,process or status measurements, and data from monitoring components maybe used to monitor conditions in, around, and on process equipment.Signals, measurements, and/or data generated or recorded by monitoringcomponents may be collected, processed, and/or transmitted through oneor more networks or connections that may be private or public, generalor specific, direct or indirect, wired or wireless, encrypted or notencrypted, and/or combination(s) thereof; the specification is notintended to be limiting in this respect.

Signals, measurements, and/or data generated or recorded by monitoringcomponents may be transmitted to one or more computing devices orsystems. Computing devices or systems may include at least one processorand memory storing computer-readable instructions that, when executed bythe at least one processor, cause the one or more computing devices toperform a process that may include one or more steps. For example, theone or more computing devices may be configured to receive, from one ormore monitoring component, data related to at least one piece ofequipment associated with the process. The one or more computing devicesor systems may be configured to analyze the data. Based on analyzing thedata, the one or more computing devices or systems may be configured todetermine one or more recommended adjustments to one or more parametersof one or more processes described herein. The one or more computingdevices or systems may be configured to transmit encrypted orunencrypted data that includes the one or more recommended adjustmentsto the one or more parameters of the one or more processes describedherein.

Examples are provided below so that the invention may be described morecompletely. These examples are only by way of illustration and shouldnot be interpreted as a limitation of the broad scope of the invention,which is set forth in the appended claims.

Patterns presented in the following examples were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “i_(O)” being theintensity of the strongest line or peak, and “I” being the intensity ofeach of the other peaks. As will be understood by those skilled in theart the determination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. In some of the x-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, and w, which represent very strong, strong, medium,and weak, respectively. In terms of 100(I/I₀), the above designationsare defined as:

-   -   w=0.01-15, m=15-60: s=60-80 and vs=80-100

In certain instances, the purity of a synthesized product may beassessed with reference to its x-ray powder diffraction pattern. Thus,for example, if a sample is stated to be pure, it is intended only thatthe x-ray pattern of the sample is free of lines attributable tocrystalline impurities, not that there are no amorphous materialspresent. As will be understood to those skilled in the art, it ispossible for different poorly crystalline materials to yield peaks atthe same position. If a material is composed of multiple poorlycrystalline materials, then the peak positions observed individually foreach poorly crystalline material would be observed in the resultingsummed diffraction pattern. Likewise it is possible to have some peaksappear at the same positions within different, single phase, crystallinematerials, which may be simply a reflection of a similar distance withinthe materials and not that the materials possess the same structure.

Example 1

Ammonium metatungstate hydrate (17.68 g, 0.07 moles of W) and ammoniumcarbonate (24 g, 0.25 moles were thoroughly mixed together in a sealedvessel at room temperature for 24 hrs. Nickel nitrate hexahydrate (29.1g, 0.1 moles of Ni) and DI H₂O (5 g) were added and the resultantmixture was continually mixed for 24 hrs at room temperature beforebeing heat treated at 95° C. for 24 hours in an open vessel withintermittent mixing. After 24 hours, the material was mixed into a finepowder and dried at 100° C. for a further 24 hours. The resultingproduct was analyzed by X-ray powder diffraction, and the X-ray powderdiffraction pattern is shown in the FIGURE.

Example 2

Nickel nitrate hexahydrate (20 g, 0.069 moles), Ammonium metatungstatehydrate (25.2 g, 0.1 moles of W), ammonium carbonate (24 g, 0.25 moles)and de-ionized (DI) water (5 g) were thoroughly mixed together at roomtemperature over 24 hrs. The resultant mixture was transferred toPTFE-lined stainless steel digestion vessel and subsequently heattreated at 105° C. for 72 hours. The product was then dried at 110° C.for a further 24 hours. The resulting product was analyzed by X-raypowder diffraction, and the X-ray powder diffraction pattern is shown inthe FIGURE.

Example 3

Ammonium metatungstate hydrate (20.16 g, 0.08 moles of W) and ammoniumcarbonate (24 g, 0.5 moles of NH₃) were thoroughly mixed together inPTFE-lined stainless steel digestion vessel for 24 hours. After whichtime, nickel nitrate hexahydrate (29 g, 0.1 moles of Ni) and zincnitrate hexahydrate (2.97 g, 0.01 moles of Zn) were added to themixture. The resultant slurry was then heated treated at 90° C. for 24hours, and then dried at 100° C. for a further 24 hours. The resultingproduct was analyzed by X-ray powder diffraction, and the X-ray powderdiffraction pattern is shown in the FIGURE.

Example 4

Ammonium metatungstate hydrate (37.87 g, 0.15 moles of W) and ammoniumcarbonate (24 g, 0.25 moles were thoroughly mixed together in a sealedvessel at room temperature for 72 hrs. Cobalt nitrate hexahydrate (29.1g, 0.1 moles of Co) and DI H₂O (7 g) were added and the resultantmixture heat treated at 90° C. for 48 hours in an open vessel withintermittent mixing. After 24 hours, the material was mixed into a finepowder and dried at 100° C. for a further 24 hours. The resultingproduct was analyzed by X-ray powder diffraction, and the X-ray powderdiffraction pattern is shown in the FIGURE.

EMBODIMENTS

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a crystalline transition metaltungstate material having the formula A_(m)M(OH)_(x)W_(y)O_(z).nH₂Owhere ‘A’ is selected from NH₄ ⁺, H₃O⁺ or combinations thereof; ‘m’varies from 1 to 12; ‘x’ varies from 0.001 to 2; ‘M’ is a metal selectedfrom Mn, Fe, Co, Ni, V, Cu, Zn and combinations thereof; ‘y’ varies from0.5 to 6; ‘z’ is a number which satisfies the sum of the valency of thecationic species present in the material; the material furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A:

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w

An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the first embodiment in this paragraphwherein the crystalline transition metal tungstate material is presentin a mixture with at least one binder and wherein the mixture comprisesup to 25 wt-% binder. An embodiment of the invention is one, any or allprior embodiments in this paragraph up through the first embodiment inthis paragraph wherein the binder is selected from the group consistingof silicas, aluminas, and silica-aluminas. An embodiment of theinvention is one, any or all prior embodiments in this paragraph upthrough the first embodiment in this paragraph wherein M is nickel orcobalt. An embodiment of the invention is one, any or all priorembodiments in this paragraph up through the first embodiment in thisparagraph wherein M is nickel.

A second embodiment of the invention is a method of making a crystallinetransition metal tungstate material having the formulaA_(m)M(OH)_(x)W_(y)O_(z).nH₂O where ‘A’ is selected from NH₄, H₃O⁺ orcombinations thereof, ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof; ‘y’ varies from 0.5 to 6; ‘z’ is a number whichsatisfies the sum of the valency of the cationic species present in thematerial; the material further characterized by a x-ray powderdiffraction pattern showing peaks at the d-spacings listed in Table A

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 wthe method comprising forming a reaction mixture containing sources ofA, M, and W; reacting the reaction mixture at a temperature from about60° C. to about 110° C. in an autogenous environment; and recovering thecrystalline transition metal tungstate material. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph further comprisingremoving at least some of the NH₄ ⁺ or the H₃O⁺ or both to form anintermediate before reacting the reaction mixture at a temperature fromabout 60° C. to about 110° C. in an autogenous environment An embodimentof the invention is one, any or all of prior embodiments in thisparagraph up through the second embodiment in this paragraph wherein thereacting is conducted for a period of time from about 30 minutes to 14days. An embodiment of the invention is one, any or all of priorembodiments in this paragraph up through the second embodiment in thisparagraph wherein the recovering is by filtration or centrifugation. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the second embodiment in this paragraphfurther comprising drying the recovered crystalline transition metaltungstate material at a temperature from about 100° C. to about 350° C.for about 30 minutes to about 48 hours. An embodiment of the inventionis one, any or all of prior embodiments in this paragraph up through thesecond embodiment in this paragraph further comprising adding a binderto the recovered crystalline transition metal tungstate material. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the second embodiment in this paragraphwherein the binder is selected from the group consisting of aluminas,silicas, and alumina-silicas.

A third embodiment of the invention is a process comprising contacting amaterial with a sulfiding agent to convert at least a portion of thematerial to metal sulfides and contacting the metal sulfides with a feedat conversion conditions to generate at least one product, wherein thematerial comprises a crystalline transition metal tungstate materialhaving the formula A_(m)M(OH)_(x)W_(y)O_(z).nH₂O where ‘A’ is selectedfrom NH₄ ⁺, H₃O⁺ or combinations thereof, ‘m’ varies from 1 to 12; ‘x’varies from 0.001 to 2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn and combinations thereof; ‘y’ varies from 0.5 to 6; ‘z’ is anumber which satisfies the sum of the valency of the cationic speciespresent in the material; the material further characterized by a x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 wAn embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the third embodiment in this paragraphwherein the conversion process is hydroprocessing. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the third embodiment in this paragraph wherein the conversionprocess is selected from the group consisting of hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the third embodiment inthis paragraph wherein the crystalline transition metal tungstatematerial, or at least a portion of the metal sulfides, or both arepresent in a mixture with at least one binder and wherein the mixturecomprises up to 25 wt-% binder. An embodiment of the invention is one,any or all prior embodiments in this paragraph up through the thirdembodiment in this paragraph, further comprising at least one of sensingat least one parameter of the process and generating a signal or datafrom the sensing; or generating and transmitting a signal; or generatingand transmitting data.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and,all parts and percentages are by weight, unless otherwise indicated.

The invention claimed is:
 1. A crystalline transition metal tungstatematerial having the formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂O where ‘A’ is selected from NH₄, H₃O⁺ orcombinations thereof; ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof, ‘y’ varies from 0.5 to 6; and ‘z’ is a numberwhich satisfies the sum of the valency of the cationic species presentin the material; the material further characterized by a x-ray powderdiffraction pattern showing peaks at the d-spacings listed in Table A:TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w


2. The crystalline transition metal tungstate material of claim 1wherein the crystalline transition metal tungstate material is presentin a mixture with at least one binder and wherein the mixture comprisesup to 25 wt-% binder.
 3. The crystalline transition metal tungstatematerial of claim 2 wherein the binder is selected from the groupconsisting of silicas, aluminas, and silica-aluminas.
 4. The crystallinetransition metal tungstate material of claim 1 wherein M is nickel orcobalt.
 5. The crystalline transition metal tungstate material of claim1 wherein M is nickel.
 6. A method of making a crystalline transitionmetal tungstate material having the formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂O where ‘A’ is selected from NH₄, H₃O⁺ orcombinations thereof, ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof, ‘y’ varies from 0.5 to 6; and ‘z’ is a numberwhich satisfies the sum of the valency of the cationic species presentin the material; the material further characterized by a x-ray powderdiffraction pattern showing peaks at the d-spacings listed in Table A:TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w

the method comprising: a. forming a reaction mixture containing sourcesof A, M, and W; b. reacting the reaction mixture at a temperature fromabout 60° C. to about 110° C. in an autogenous environment; and c.recovering the crystalline transition metal tungstate material.
 7. Themethod of claim 6 further comprising removing at least some of the NH₄or the H₃O⁺ or both to form an intermediate before reacting the reactionmixture at a temperature from about 60° C. to about 110° C. in anautogenous environment.
 8. The method of claim 6 wherein the reacting isconducted for a period of time from about 30 minutes to 14 days.
 9. Themethod of claim 6 wherein the recovering is by filtration orcentrifugation.
 10. The method of claim 6 further comprising drying therecovered crystalline transition metal tungstate material at atemperature from about 100° C. to about 350° C. for about 30 minutes toabout 48 hours.
 11. The method of claim 6 further comprising adding abinder to the recovered crystalline transition metal tungstate material.12. The method of claim 11 wherein the binder is selected from the groupconsisting of aluminas, silicas, and alumina-silicas.
 13. A conversionprocess comprising contacting a material with a sulfiding agent toconvert at least a portion of the material to metal sulfides andcontacting the metal sulfides with a feed at conversion conditions togenerate at least one product, wherein the material comprises acrystalline transition metal tungstate material having the formula:A_(m)M(OH)_(x)W_(y)O_(z) .nH₂O where ‘A’ is selected from NH₄, H₃O⁺ orcombinations thereof; ‘m’ varies from 1 to 12; ‘x’ varies from 0.001 to2; ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn andcombinations thereof, ‘y’ varies from 0.5 to 6; and ‘z’ is a numberwhich satisfies the sum of the valency of the cationic species presentin the material; the material further characterized by a x-ray powderdiffraction pattern showing peaks at the d-spacings listed in Table A:TABLE A d(Å) I/I₀ (%) 11.84 s 10.52 vs 7.79 w 7.59 w 6.81 w 6.48 w 6.18w 5.93 w 5.70 w 5.59 w


14. The process of claim 13 wherein the conversion process ishydroprocessing.
 15. The process of claim 13 wherein the conversionprocess is selected from the group consisting of hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.
 16. The process of claim 13 wherein the crystallinetransition metal tungstate material, or at least a portion of the themetal sulfides, or both are present in a mixture with at least onebinder and wherein the mixture comprises up to 25 wt-% binder.
 17. Theprocess of claim 13 further comprising at least one of: sensing at leastone parameter of the process and generating a signal or data from thesensing; or generating and transmitting a signal; or generating andtransmitting data.